Process for polymerizing dienes



United States Patent'O PROCESS FOR POLYMERIZING DIENES Charles E. Brockway, Akron, and Albert F. Ekar, Cleveland, Ohi'o, assignors to Goodrich-Gulf Chemicals, Inc., Cleveland, Ohio, a corporation of Delaware No Drawing. Filed Nov. 7, 1956, Ser. No. 620,810

4 Claims. c1. 260--94.3)

' produce polymers of increased molecular weight and/or reduced gel content.

Butadiene and isoprene have been polymerized in hydrocarbon solution in the presence of precipitate-containing heavy metal/organometallic catalysts with the production of homopolymers of great regularity of structure wherein the monomer units are united in an all-1,4 structure. In the copending application of Samuel E. Horne, Jr., Serial No. 472,786, filed December 2, 1954, there is disclosed the preparation of an all-cis 1,4 polyisoprene by such a process. In the copending application of Carlin F. Gibbs, Serial No. 503,027, there is disclosed the production of many polymers of this type, including specifically an all-trans 1,4 polyisoprene; In the copending application of Earl J. Carlson, Serial No. 503,028, filed April 21, 1955, there is disclosed the preparation of all-1,4 polybutadienes, including specifically. an all-trans 1,4 polybutadiene.

In the above-described processes control of the polymerization can be effected to some degree by varying temperature, catalyst concentration and the catalyst molar ratio heavy metal/organometallic compound, and monomer/solvent ratio. Such control is not sufficient or practical in all cases for commercial scale operations. For example, while the molecular weight of the polymers are comparable to those of other known synthetic'rubbers, it is desirable in rnariy cases to produce polymers of con: siderably higher molecular and/or lower gel content.

More specifically,

With only the above-mentionedcontrol factors avail- V able, abnormally low reaction'temperatures, high catalystlevels, and exceptional solvent and monomer purity are required for a noticeably increased molecular weight. Likewise, the polymers generally contain a certain amount of gel which, it appears, may be bad for stress crack and out growth. It would be highly advantageous to be able to modify the course of the polymerization by the simple expedient of adding a substance to the reaction mixture (as is done in aqueous emulsion, free radical catalyzed polymerizationprocesses).

In accordance with this invention there is provided a method of carrying out the polymerization of conjugated polyolefin hydrocarbons, as definedbelow, in the presence of (l) a heavy metal/organometallic catalyst and (2) a soluble organo-silicon compound containing siliconoxygen bonds. It has'been found that very small amounts of silicone oils or greases, silicate esters and various hydrolyzed silane derivatives have the ability to modify the course of the polymerization reaction producing polythem of substantially increased molecular weights, re-Y In addition, reaction modifyinggaction of the organo=silicon modifiers are the 'T 2,911,349 Patented precipitate-containing catalysts produced by the interac-f tion of (I) an organo-metallic compound (or compound I containing at least one metal-carbon bond) with (2 1 compound of a heavy metal of the 4th to the 10th posi tions of the periodic chart in which the elements are'ar ranged in short and long periods and in whicli the alkali metals occupy the first position (see the Periodic Chartof the Elements, on pages 342-343 of the 33rd Edition of the Handbook of Chemistry and Physics, published 1951 by the Chemical Rubber Publishing Co., Cleveland, Ohio). Such metals are those of periodic groups IVB, VB, VIB, VIIB, and VIII including titanium, zirconium, hafnium, vanadium, niobium (columbium), tantalum, chromium, molybdenum, tungsten, manganese, masurium, rhenium', iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, and platinum, as well as metals im 4 corresponding positions in the last long period in' the. socalled actinium series suchas thorium and uranium. While any compound of these metals, whether soluble or insoluble, can be employed, it is preferred to employ those that are anhydrous salts of the formula M(A),,,, wherein M is the heavy metal atom, A is a monovalent anion (preferably non-oxidizing in character) and n'is one of the higher valence'states of the metal, preferably the highest. Especially preferred are the anhydrous halides (chlorides, bromides, iodides and fluorides) of these metals. The tetrachloride of titanium is preferred. for the preparation of all-cis 1,4 and all-trans 1,4 poly isoprenes; the tetrachloride of vanadium and the dichlo ride of nickel are preferred for all-trans 1,4 polybutadiene' and for all-trans 1,4 polyisoprene; and the dichloride of cobalt for all-eis 1,4 polybutadiene Other useful heavy metal salts include the inorganic salts such, as the oxyhalides and sulfates and other organic salts such as ace! tates, acetylacetonates and oxalates of the .heavy metals of the above-defined groups. 1

As pointed out above, the heavy metal compounds are converted into active, directive catalysts by interaction with a correct proportion of an organo-metallic compound containing atleast one carbon-to-metal linkage, that is, a metal atom attached to an organic group through r a carbon-to-metal linkage. Such organo-metallic com pounds include alkali-metal hydrocarbyls; alkaline-earth hydrocarbyls; similar compounds of magnesium and zinc; aluminum hydrocarbyls; and complexes ofone orrn'ore. of these and/ or with still other metals. The term fhydro-j car-byl is employed herein to mean any compound where in'a hydrocarbon radical (hence the term hydrocarbyl" including aliphatic cycloaliph'atic and aromatic ,h yd r' carbon radicals, is attached to a metal through aflcarbon atom. Thus, there may be utilized sodium, potassium, and lithium alkyls, magnesium alkyls, zinc alkyls," lead" alkyls, tin alkyls, aluminum alkyls, aluminum aryls, aluminum aralkyls, aluminum alkaryls, complexes suc as sodium aluminum tetrabutyl, and many others.

Greatly preferred are theorganO aIuminumEompou (aluminum hydrocarbyls) of the structure I J B III V I i wherein R is a hydrocarbon radical, R is another R group, an OR group, a hydrogen atornor a haloge atom, and R' is another R' or hydrogen.-']Particu preferred arethe aluminum tri-(alkyl) 5 hydroca such as triethyl aluminum, trip-ropyl-aluininum butyl aluminum, triisobutyl aluminum, V andthelike. 'Thecatalyst-forming reaction betwee compound and the organo-meta' amines, and any other substance containing active hydro- 'gen or otherwise capable of preferential reaction with the organo-metallic portion of the catalyst or with any of the organo-metallic catalyst-forming ingredients. Reaction usually is accompanied by a change in color and/or the formation of a precipitate. The temperature of reaction is not critical up to 80 to 100 C. (where some organo-metallic compounds may decompose), although with the more insoluble, less reactive heavy metal compounds it is sometimes advantageous to heat the reaction medium to speed an otherwise slow reaction. With the more active alkyl aluminum compounds and solvent-soluble heavy metal compounds such as TiCl the reactions are vigorous at room temperature (and slightly exo thermic). The latter catalysts can be utilized without aging while the slower reacting catalysts can be improved and rendered more predictable by aging'for a time before being brought into contact with the monomer. In many cases it is advantageous to minimize the effects of oxygen and water, etc. by adding a sufficient proportion of the organo-metallic compound to a small portion of the solvent (to scavenge impurities), then add the heavy metal compound to form the catalyst, and finally dilute the already-formed catalyst to the desired final concentration before or after adding the monomer. Catalyst aging and mixing while in concentrated form aid in achieving a stable equilibrium condition in the catalyst, thereby rendering the action of the catalyst more predictable.

The organo-silicon modifier preferably is present during the catalyst-forming reaction in order to secure maximum modifier action. The presence of the organo-silicon derivative does not interfere with the catalyst-forming reaction and, as far as is known, does not participate therein. However. when present it can be envisioned that the modifier is adsorbed on the surface of the freshlyformed catalyst precipitate and thereby is rendered more effective. However, any order of mixing can be employed.

The proportion of organo-silicon modifier may be varied somewhat but, in general, only very small proportions are required. At least about 0.1 percent by weight based on the weight of monomers should be utilized to secure a significant modifying effect. As the proportion of modifier is increased, the modifying action also increases. up to a concentration of about 0.2 to 0. percent. Beyond the latter value little additional modifying action is obtained. Beyond about 0.5 percent retardation of the polymerization reaction may be too severe to obtain good reactions in a practical time. In some cases an increase in total catalyst concentration can be employed to improve reaction rate without serious interference with the action of the modifier. However, it is generally preferred to employ as small a proportion of modifier as is consistent with a good balance of high reaction rates, good conversion and the desired increase in molecular weight, reduction in gel content, etc.

It is generally desirable to carry out both the catalystforming reaction and the subsequent polymerization reaction in an inert diluent media such as any of the aliphatic, cycloaliphatic and aromatic hydrocarbons including the saturated alkanes such as butane, hexane, pentane, heptane, cetane, or the like or mixtures thereof such as Deobase kerosine, diesel oil, or the mixture of alkanes obtained from the Fischer-Tropsch process: or a'cycloalkane such as cyclohexane or methyl cyclohexane; or a benzene hydrocarbon such as benzene, toluene or xylene. In some cases unsaturated hydrocarbons can be used as diluents where such do not readily form copolymers with the diene pol merized. It is important that the inert hydrocarbon diluent be as low as possible in free water and oxygen. Flash distillation followed by storage over a drying agent such as CaH BaO, molecular-sieves, sodium hydride, metallic sodium, etc. will "reduce the water content'to a verylow figureof or p.p.m.'or less. Treatment with powerful drying agents such-as me,-

tallic sodium in dispersed form, molecular sieves etc. followed by flash-distilling also is effective in removing water and oxygen. It sometimes is helpful to add the solvent to the reactor and then distill a portion of the solvent to remove excess water.

In general, the polymerization process of this invention is also sensitive to monomer impurities. For example, commercial isoprene contains cyclopentadiene and acetylenic hydrocarbons which are powerful retarders. Treatment with sodium, maleic anhydride, molecular sieves, or careful azeotropic distillation with pentane is helpful in reducing the proportion of these inhibitory or retarding substances. Commercial butadiene, on the other hand, seems to be free of such substances and seems to require only flash-distillation to remove the monomer inhibitor, if any, peroxides, or excess water and oxygen.

The proportion, or ratio, of heavy metal to organometallic compound employed to produce the catalyst can be varied considerably with the obtaining of changes in polymerization reaction rate, conversion and, in certain cases, changes in polymer structure. For example, with the TiCh/triisobutyl aluminum system, all-trans 1,4 polyi'soprenes are obtained in range of Ti/Al (molar ratio) of from about 1.5 :1 to about 3:1, most preferred being about 2:1. All-cis 1,4-polyisoprenes are obtained in the range from about 0.5 :1 to 1.5 :1, most preferably about 1:1. When working with butadiene as the monomer, the Ti/Al molar ratio of between about 1.5 :l and about 3:1 will produce an all-trans 1,4 polybutadiene. With a Ti/Al ratio of 3:1 and heating the catalyst at about 50-l00 C. for several hours an essentially all-cis 1,4 polybutadiene can be obtained.

With the catalyst combination CoCl /triisobutyl aluminum, an all-cis 1,4 polybutadiene is obtained with catalysts in which the Co/Al molar ratio is between about 25:1 to about 1:25, although better yields are obtained in the range between about 25:1 and about 1:1 (best 5:1). All-trans 1,4 polybutadienes are obtained with a VCl /triisobutyl aluminum molar ratio of between a out 1:1 to 1:20. In the system Nicl /triisobutyl aluminum all-trans 1,4 polybutadienes are obtained at Ni/Al ratios of between about 10:1 to about 1:10. With other heavy metal compounds and/or other organometallic compounds, the ratio heavy metal/organometallic compound usually will have to be adjusted to bring about the proper reduction of the heavy metal in order to secure a catalyst capable of the desired form of directive activity. The organo-silicon modifier has no effect on the directive activity of any of these heavy metal/organometallic catalysts.

The total concentration (i.e. total of both ingredients) of catalyst can be varied widely depending on, to a considerable extent, the solvent and monomer purity. With these cataysts, the total concentration may vary from as little as about 0.25 to 0.5 percent to as high as 20 percent or more, although from about 1 to about 7 percent will usually suffice. In terms of molar quantities, from about 3 or 5 to 100 millimoles per liter of total catalyst will usually sufiice.

After the catalyst has been prepared, the monomer is added (although any order of mixing can be employed and the monomer can be present during the catalyst preparation step) and the resulting mixture heated or cooled, as may be required, to control the polymerization reaction rate at a reasonable value. Agitation should ordinarily be employed for good heat transfer in order to assist in reaction control. With the organo-silicon modifiers of this invention, the use of reaction temperatures in excess of about 35 C. is not desirable since higher temperatures seem to reduce the modifying effects of the modifier. It is preferred to control'the polymerization temperature at a value below about 25 C.

5 ferred to operate in the range from about -5 to about 25C. v

Under the above conditions the reactionis usually complete in less than 48 hours and reaction times of a matter of minutes or an hour or two can be obtained, if desired. Due to the inherently poor heat transfer coefficient in such a system (oil-to-metal) and the tendency for the medium to become viscous (the productin most cases is a quite viscous cement-like solution of polymer) during the course of the reaction, reaction times of from 10 to hours are much more easily controlledin com: mercial scale, batch-type equipment.

The relative proportions of solvent or diluent and monomer may also vary quite widely, although because of the aforementioned viscosity increase during polymerization the proportion of monomer will usually be less than that of the solvent or diluent. It is generally desirable to employ a solventzmonomer (volume) ratio of from about 5:1 to about 3,021 or1more, most preferably from about 7:1 to 15:1. With such systems, and when producing diene polymers of molecular weight above about 50,000 operation at final solids levels of from about 5 to about 10 percent is practical.

The monomers which are polymerized according to this invention are hydrocarbon in nature and constitute the ,classofconjugated polyolefin hydrocarbons. In the process of this invention such monomers are not only converted to polymers having new and'improved proper: ties by reason of their containing essentially all of the units derived from conjugatedpolyolefin hydrocarbons present in a desired geometric isomeric configuration, for example in an all 1,4 structure, and in a desired stereo isomeric configuration, for example cis-l,4 or trans-1,4, but alsoby reason of their being possessed of markedly higher molecular weights and/or lower gel contents, as compared to analogous polymers prepared in the absence of the organo-silicon modifier.

The monomeric hydrocarbon material which is poly merized according to this invention may be a single conjugated polyolefin hydrocarbon or it may be a mixture of any two or more'of such conjugated polyolefin hydrocarbons, or it may be mixture containing a significant proportion of a conjugated hydrocarbon together with one or more other polymerizable hydocarbons including both monoolefin hydrocarbons and non-conjugated poly olefin hydrocarbons. metal/organometallic catalysts is their ability to combine dissimila r tnonomeric units with each unit responding in its own unique fashion to the directive influence; of the catalyst. ::Thus for example, butadiene-l,3; hydr.o carbons polymerized with a 1,4' activecatalyst .will be found to be present in copolymers as 1,4 units irrespective ofthe presence or absence of other'monomers, ,even when the latter are monoolefinic hydrocarbons,

The conjugated polylefin hydrocarbon preferably is a conjugated diolefin hydrocarbon such as butadienetthe simplest of the series) or a methyl-substituted butadiene 1,3, that is, isoprene or piperylene;'or it may be a conjugated aliphatic diolefin containing more than five car,- bon atoms acontaining not more/than onehydr ogarbgtl substituent andthat attached to the ,2-carbon atom including 2-ethy1-butadiene-l,3, 2-propyl'-butad,i ene-'l,3,2 phenyl-butadiene-l ,3, Z-neopentybbutadiene-1 ;3 and many others; In addition other monomerjcconjugated poly olefin hydrocarbons which maybe polymerized include A surprising feature of the heavy I a dark,'brownish"blackprecipitate.

hexadiene-2.4, hexatriene-1,3,5, myrcene, alloocimine and jWhenthe monomeric hydrocarbon material is a mix:-

ture .ofja conjugated polyolefin. hydrocarbon, iprefieraibly ac niug tedrdiqlcfin, wi anot er t p 9 .;hydr,;

monomer; ;;the other: hydrocarbon may be monoolefin such-as ethylene, propylene, butene l,-,;jg9g

butene, or any of the various pentenes, hexenes,-octel!e i,

decenes, etc. whetherjstrai'ght-chained or branched, 01 I it may, beanalicyclic monoolefin such as cyclohexenegf cycloheptene, and the like, or it may be an aryl-substituted monoolefin such as styrene, alpha-methyl styrene; jo -,-"n'|- and p-methyl styrenes, dimethyl styrenes, indene,:vinyl;

naphthalene, allyl benzene, and many others. In addi tion the monomeric material may be a mixture. ofaeon; 1 jugated polyolefin with a non-conjugated polyolefin such as allene, diallyl, .dimethallyl, propyl allene, squalene, 1-

vinyl-cyclohexene-3, divinyl benzene and others. Greatly preferred are the butadienes-l,3 hydrocarbons containing not more than one substituent and that on the 2 carboii atom.

. The invention materially increased molecular weight as compared with acontr'ol polyisoprene concurrently prepared in the same fashion but without the silicone ingredient. The experi ments are conducted in 1 quart glass beverage bottles whichjfirst are washed clean, dried in a high temperature air, overtarid allowed to cool under a current of dry}. oxygen-free nitrogen; fln-cha rging the bottles the nitro gen flow is continued at all times until the bottleis sealed. First, the ben zen'e't440 grams or 500 ml.) and isoprene (39.5 grams) are combined. Then the triisobutyl aluminum (0.92 ml. or about 6.5 millimoles per liter of 7 charge) isaddedfollowed by a piece of silicone labora' tory stop cock greaseof about 0.2 gramand thebot tle contents agitated until the grease dissolves. 0.36 ml. of TiCI are added and the bottle swirled to eife ct mixing. 1 At this point the Ti/Alratio is 0.9:1j'with a titanium concentration of 5.85 millimoles per liter (mM./liter). Thecatalyst rapidly forms in the form-of The' bottle is then sealed and placed in a rack rotating end-over-end in 'a 5' C. water bath. A control, prepared in the same fashion but without the silicone, is charged at the same tin" No sign ofpolymerization isfnoted in the 'silicone containing bottleuntil'aft'er about 8 hours whereas the control bottlejshows a vigorous reaction after abouto ne hour. 'Atthe end of about hours the reactions are adjudged to have gone as far as they will go. The contents of both bottles then are observed to have subst'an tially thickened and both are seen to contain viscous cement-like solutions of polymer, the control being so thick as to be scarcely able to flow. At this point, the

bottles are removed from the bath, flushed with dry nitrothe mixture has been agitated to disperse the shortstop solution somewhat, [5 ml. of an antioxidantdispersion containing 8 ,grams, of Agerite White".,,(sym-di.-betanaphthyl-para phenylenediarnine), 4 grams of VDH ('diphenyll-para-phenylenediamine), and 200 ml. of ben-' zene are added. The bottles are then rescaled and placed back in the water bath for both addedsolutionsto disperse themselves. The polymer cements arenoticcably thinned by this treatment and the bottle'contentsrcan fbe;

discharged into a closed vessel each-containing 400ml; of a 3:1 (by volume) 'mixtureof benzene and methanol.

A thin, ;homoge neous solution results in eachr ca e t o' which rnall proportion Lot pure methanol is add will now be more tantra-seated with reference to several specific examples which are intended The resulting polymers are then subjected to a sol-gel determination with the following results:

Conver- Sample sinn at Percent Swelling Intrin ic 70 hrs., Gel lurlex Viscosity percent Silicone-modified 57 7 97 5. 55 Control 97 10 66 3. S2

Infrared examination of the two samples employing the method of R. R. Hampton (Analytical Chemistry, August 1949, page 923) reveals that both samples are all-cis 1,4 polyisoprenes (i.e. at least 95% cis 1,4 units) with substantially no units derived from 1,2 or 3.4 addition. In the above sol-gel data it is clear that the silicone stop cock grease materially modified the course of the polymerization in the experimental bottle charge. The increase in I.V. from 3.82 to 5.55 is a marked improvement to be derived from the addition of such a small amount (0.5%) of the modifier. While the reduction of the gel content from 10 to 7% is a difference within the limits of experimental error, subsequent experiments will demonstrate quite consistently that the gel content of the polymer is generally lower and that such an effect is more noticeable in solvents which produce more highly gelled polymers.

While it will be noted that the silicone stop cock grease retarded the polymerization, subsequent examples will show that this retarding action can be partially overcome by the use of increased catalyst levels. The important feature of the data of Example I is that a marked increase in molecular weight can be obtained without a corresponding increase in gel content.

The silicone-modified polymer of Example I is found to mill just as easily as the control polymer. This is as expected since the gel content is lower. When vulcanized the silicone-modified polymer has excellent properties.

Example II Conver- Pcrcent: Modifier sion at Percent Swelling Intrinsic 116 hrs.. Gel Index Viscosity percent grease, 0.5% 40 12 92 5.33 oil, 0.5% 32 17 83 5. 60

In a comparable run, 05 percent of the same silicone grease is added as the last component of the charge (after preparation of the catalystand addition of monomer) the reaction is much faster and the intrinsic viscosity is only 3.34. V

Example III As pointed out in Example I, the reaction times of 70 hours (Ex. I) or 116 hr. (Ex. II) are too slow for commercial utility. In this example, the procedure of Exarnple I is repeated a number of times employing a level of .triisobutyl aluminum of.7.75 .mM./liter and a TiCl level of 7.0 mM./liter (Ti/Al=0.9 1'). At'the same time,

varying amounts of the methyl silicone oil of Example II are included to determine whether an optimum exists. In this case much higher conversions are reached in only 46 hours. Sol-gel data are as follows:

Silicone Oil. Wt. Time, Conver- Percent Swelling Intrinsic Percent on Monomer Hrs. sion, rier- Gel Index Viscosity cen It is evident that from about 0.1 to about 1.1 percent silicone oil has a pronounced effect on the molecular weight of the polymer. It is also evident that from about 0.1 to 0.4 percent better reaction rates and maximum I.V. are obtained. With as little as 0.1 to 0.25 percent, 60 to 80 percent conversion are obtained with maximum gain in molecular weight.

Example IV The procedure of Example III is repeated but at a temperature of 50 C. instead of 5 C. The control made without the silicone oil proceeds to an I.V. of only 2.26 while with 0.1-to 0.4 percent of the silicone oil the I.V. is about 2.50 in all cases. While the effect of temperature is strong, it evidently does not completely overcome the molecular weight building ability of the silicone oil.

Example V Time, Percent Percent Swelling Intrinsic Percent Silicone Oil Hrs. Conver- Gel Index Viscosity sion it is evident that butane produces a more highly gelled polymer than does benzene. However, this tendency is shown to be overcome to a large degree by the addition of silicone oil. In addition, a valuable increase in molecular weight is achieved. In all cases, the polymers obtained are ail-cis l,4 polyisoprenes.

It should be noted, that to achieve an I.V. of over 4 (i.e. without silicone) in the butane system it is necessary to carry out the polymerization at temperatures as low as -20 C. and to utilize the purest grades of butane and isoprene in order to achieve a practical reaction rate. Even so. such a reaction requires 89 hours to reach a conversion of over 80 percent and the polymer obtained will contain 25 percent gel or more. It is clear that the use of silicone oil in butane at 5 C. is a better mode of operation when a high molecular weight, low-gel polymer is desired.

Example VI In this example, tetra-ethyl silicate and diphenyl silanediol are utilized as the organo-silicon modifiers at levels of 0.1 percent and 0.2 percent my weight on the monomeric isoprene. The solvent is benzene, the TiCl; level is 7.0 mM./liter, the Ti/Al ratio is 0.921, and the reaction is conducted for 17.8 hours at 5 C. The polymer cements are treated in each case with a solution containing 5 m1. of'triethylamine, 20 m1. of methanol, and

80 ml. of benzene and then worked up as in Example I. The data on these polymers are as follows:

While the I.V. of all the polymers are somewhat low, both tetra-ethyl silicate and diphenyl silanediol seem to have less efiect on reaction rate while favoring increased molecular weights.

From the experiments described in Examples I to VI, it is seen that the efir'ect of an organo-silicon compound enables one to duplicate the effects of low temperature reactions without the use of expensive, extra-low temperature refrigeration equipment.

While we have disclosed certain preferred manners of performing an invention, we do not desire or intend to limit ourselves solely thereto, for the precise proportions of the materials utilized may be varied and equivalent chemical materials may be employed, without departing from the spirit and scope of the invention as defined in the appended claims.

We claim:

1. The method of polymerizing monomeric isoprene to obtain an essentially all 1,4 polymer comprising combining said monomeric isoprene with a reaction medium containing an inert hydrocarbon diluent and from about 0.5 to about 7 %/wt. of a catalyst prepared by combining (1) a trialkyl aluminum, (2) from about 0.1 to about 0.5% by weight on said isoprene of a methyl silicone oil, and (3) titanium tetra-chloridefsaid ingredients (1) and (3) being combined in a molar ratio TizAl of between about 0.5 :1 to about 15:1, and carrying-out the polymerization of said isoprene in said medium at a temperature between about 5 and about 25 C.

2. The method of claim 1 wherein tetraethyl silicate '9 is substituted for said silicone oil.

3. The method of claim 1 wherein diphenyl silanediol is substituted for said silicone oil.

4. The method of polymerizing a monomeric material selected from the class consisting of butadiene-1,3, isoprene, piperylene, 2-ethyl-butadiene-1,3, 2-propyl-butadi cue-1,3, 2-phenyl-butadiene-l,3, and 2-neopenty1-butadiene-1,3, comprising combining said monomeric material with a reaction mixture containing an inert hydrocarbon diluent and from about 0.5 to about 7%/wt. based on said monomeric material of an active catalyst prepared v V of said heavy metalzaluminum in said catalyst being,

when titanium is the heavy metal, from about 0.5 :1 to 3:1, when vanadium, from about 1:1 to about 1:20, when cobalt, from about 25:1 to about 1:25, and when nickel, from about 10:1 to about 1:10, with (3) from 0.1 to 1.1%/wt. based on the weight of said monomeric material of an organosilicon modifier soluble in said mixture and selected from the class consisting of silicone greases, methyl silicone oils, tetraethyl silicate, and diphenyl silane diol, and carrying out the polymerization of said monomeric material in said reaction mixture at a temperature from about 5", to about 35 C.

References Cited in the file of this patent UNITED STATES PATENTS 

4. THE METHOD OF POLYMERIZING A MONOMERIC MATERIAL SELECTED FROM THE CLASS CONSISTING OF BUTADIENE-1,3 ISOPRENE, PIPERYLENE, 2-ETHYL-BUTADIENE-1,3, 2-PROPYL-BUTADIENE-1,3, 2-PHENYL-BUTANDIENE-1,3, AND 2-NEOPENTYL-BUTADI ENE-1,3, COMPRISING COMBINING SAID MONOMERIC MATERIAL WITH A REACTION MIXTURE CONTAINING AN INERT HYDROCARBON DILUENT AND FROM ABOUT 0.5 TO ABOUT 7% WT. BASED ON SAID MONOMERIC MATERIAL OF AN ACTIVE CATALYST PREPARED BY COMBINING (1) AN ALUMINUM ALKYL AND (2) A COMPOUND OF A HEAVY METAL SELECTED FROM THE CLASS CONSISTING OF TITANIUM, VANADIUM, COBALT AND NICKEL, THE RATIO OF SAID HEAVY METAL: ALUMINUM IN SAID CATALYST BEING, WHEN TITANIUM IS THE HEAVY METAL, FROM ABOUT 0.5:1 TO 3:1, WHEN VANADIUM, FROM ABOUT 1:1 TO ABOUT 1:20, WHEN COBALT, FROM ABOUT 25:1 TO ABOUT 1:25, AND WHEN NICKEL, FROM ABOUT 10:1 TO ABOUT 1:10, WITH (3) FROM 0.1 TO 1.1%/WT. BASED ON THE WEIGHT OF SAID MONOMERIC MATERIAL OF AN ORGANOSILICON MODIFIER SOLUBLE IN SAID MIXTURE AND SELECTED FROM THE CLASS CONSISTING OF SILICONE GREASES, METHYL SILICONE OILS, TETRAETHYL SILICATE, AND DIPHENYL SILANE DIOL, AND CARRYING OUT THE POLYMERIZATION OF SAID MONOMERIC MATERIAL IN SAID REACTION MIXTURE AT A TEMPERATURE FROM ABOUT -5* TO ABOUT 35*C. 